Siloxanyl-containing monomers

ABSTRACT

Monomers for polymers having high oxygen permeability, high water content and a low modulus of elasticity are provided, and polymers and ophthalmic lenses comprised of said monomers are provided. They are monomers represented by formula (1) or (2) below:
 
X—O—(CH 2 CH 2 CH 2 O) m —(CH 2 ) n —A   (1)
 
     
       
         
         
             
             
         
       
         
         
           
             wherein, X is a polymerizable group having carbon-carbon unsaturated bonds; A is a siloxanyl group; R is H or a methyl group; m is an integer of 1 to 10; m′ is an integer of 2 to 10; and n is an integer of 2 to 10.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a 371 National Stage Entry of PCT InternationalApplication No. PCT/JP01/08680, filed Oct. 2, 2001.

TECHNICAL FIELD

This invention relates to monomers, polymers and ophthalmic lenses inwhich they are used. This invention is particularly suited to use inophthalmic lenses such as contact lenses, intraocular lenses andartificial corneas.

PRIOR ART

In recent years, 3-methacryloxypropyltris(trimethylsiloxy)silane hasbeen widely used for polymers having high oxygen permeability, and,particular, as a monomer for ophthalmic lenses (Japanese PatentApplication Laid-Open No. 60[1985]-142324 and Japanese PatentApplication Laid-Open No. 54[1979]-24047). However, because3-methacryloxypropyltris(trimethylsiloxy) silane has essentially nohydrophilic properties, polymers that are obtained from it have a lowwater content. This is not desirable for ophthalmic lenses. Further,polymers that are obtained from3-methacryloxypropyltris(trimethylsiloxy)silane have a comparativelyhigh modulus of elasticity so that it is difficult to use them for softcontact lenses.

A monomer represented by formula (10) below is described in, forexample, Japanese Patent Application Laid-Open No. 60[1985]-131518.

When the monomer of formula (10) is used, there is a tendency forpolymers having higher water content and a lower modulus of elasticityto be obtained than when 3-methacryloxypropyltris(trimethylsiloxy)silaneis used. However, this modulus of elasticity is not sufficient and alower modulus of elasticity is still needed.

DISCLOSURE OF THE INVENTION

This invention has the objective of solving the aforementioned problemsand of providing monomers for polymers having high oxygen permeabilityand also high water content and a low modulus of elasticity. It has thefurther objective of providing polymers comprised of said monomers, andophthalmic lenses.

In order to achieve the aforementioned objectives, the monomers andpolymers of this invention have the structure indicated below.

[1] A monomer that is represented by formula (1) or (2) below:X—O—(CH₂CH₂CH₂O)_(m)—(CH₂)_(n)—A  (1)

-   -   wherein, X is a polymerizable group having carbon-carbon        unsaturated bonds; A is a siloxanyl group; R is H or a methyl        group; m is an integer of 1 to 10; m′ is an integer of 2 to 10;        and n is an integer of 2 to 10.

[2] A polymer comprising the monomer of [1] above as a polymerizationcomponent.

EMBODIMENT OF THE INVENTION

We shall now describe the embodiment of this invention. The monomers ofthis invention are characterized in that they are represented by formula(1) or (2) below:X—O—(CH₂CH₂CH₂O)_(m)—(CH₂)_(n)—A  (1)

-   -   wherein, X is a polymerizable group having carbon-carbon        unsaturated bonds; A is a siloxanyl group; R is H or a methyl        group; m is an integer of 1 to 10; m′ is an integer of 2 to 10;        and n is an integer of 2 to 10.

In this formula, X is a polymerizable group having carbon-carbonunsaturated bonds. Specific examples can include the groups representedby formulas (4) to (9) below. Of these, the groups represented byformulas (4) and (5) are preferable from the standpoints of ease ofsynthesis and level of polymerization characteristics, and the grouprepresented by formula (5) is the most desirable:

-   -   wherein, in formulas (4) through (9), R¹ is H or a methyl group.

In formula (1) or (2), A is a siloxanyl group. The term siloxanyl groupin this specification indicates a group that has at least one Si—O—Sibond. Substituents as represented by formula (3) below are desirable foruse as siloxanyl groups:

-   -   wherein, in formula (3), A¹ to A¹¹, respectively and        independently, are H, alkyl groups of 1 to 20 carbon atoms that        may be substituted or aryl groups of 6 to 20 carbon atoms that        may be substituted; k is an integer of 0 to 200; and a, b and c,        respectively and independently, are integers of 0 to 20,        excepting the case k=a=b=c=0.

In formula (3), A¹ to A¹¹, respectively and independently, are H, alkylgroups of 1 to 20 carbon atoms that may be substituted or aryl groups of6 to 20 carbon atoms that may be substituted. Specific examples caninclude H, alkyl groups such as methyl groups, ethyl groups, propylgroups, isopropyl groups, butyl groups, isobutyl groups, sec-butylgroups, t-butyl groups, hexyl groups, cyclohexyl groups, 2-ethylhexylgroups and octyl groups and aryl groups such as phenyl groups andnaphthyl groups. Of these, methyl groups are the most desirable.

In formula (3), k is an integer of 0 to 200, preferably, of 0 to 50,and, more preferably, of 0 to 10. a, b and c are, respectively andindependently, integers of 0 to 20, and, preferably, independently andrespectively, integers of 0 to 5. When k=0, the combinations of a, b andc should be a=b=c=1, a=b=1 and c=0, and a=1 and b=c=0.

Of the substituents represented by formula (3), those that areparticularly desirable because they can be acquired comparativelycheaply on an industrial basis are tris(trimethylsiloxy)siylyl groups,methylbis(trimethylsiloxy)silyl groups, dimethyl(trimethylsiloxy)silylgroups, polydimethylsiloxane groups, polymethylsiloxane groups andpoly-co-methylsiloxane-dimethylsiloxane groups.

In formula (1), m is an integer of 1 to 10. However, from the standpointof balance of the oxygen permeability with high water content and lowmodulus of elasticity of the polymers obtained from said monomers, mshould be 1 or 2, and, most preferably, 1.

Further, in formula (2), m′ is an integer of 2 to 10. However, from thestandpoint of balance of the oxygen permeability with high water contentand low modulus of elasticity of the polymers obtained from saidmonomers, m′ should be 2 or 3, and, most preferably, 2.

In formulas (1) and (2), n is an integer of 2 to 10. From the standpointof ease of synthesis, n should be 2 or 3, and, most preferably, 3.

The following method can be presented as an example of the method ofsynthesis of the monomers represented by formula (1). First, a compoundrepresented by formula (II):H—O—(CH₂CH₂CH₂O)_(m)—H  (11)

-   -   wherein, in formula (11), m is an integer of 1 to 10 and R is H        or a methyl group,        is reacted with a compound represented by formula (12):        Z—(CH₂)_(n-2)—CH═CH₂  (12)    -   wherein, in formula (12), Z is elimination groups such as I, Br,        Cl and p-toluenesulfonyloxy groups and n is an integer of 2 to        10,        in the presence of a base such as potassium hydroxide or sodium        hydride, to obtain a compound as represented by formula (13):        H—O—(CH₂CH₂CH₂O)_(m)—(CH₂)_(n-2)—CH═CH₂  (13)    -   wherein, in formula (13), m is an integer of 1 to 10, n is an        integer of 2 to 10, and R is H or a methyl group.        Then, by reacting the compound represented by formula (13) with        a suitable compound having carbon-carbon unsaturated bonds, a        compound represented by formula (14)        X—O—(CH₂CH₂CH₂O)_(m)—(CH₂)_(n-2)—CH═CH₂  (14)        is obtained. The suitable compound having carbon-carbon        unsaturated bonds differs depending on the type of X. For        example, when X is a group represented by formula (4), it is the        corresponding epoxy compound, when X are groups represented by        formula (5), formula (8) and formula (9), it is the        corresponding halide and when X are groups represented by        formula (6) and formula (7), it is the corresponding isocyanate        compound. Next, a compound as represented by formula (14) is        reacted with a compound as represented by formula (15)

in the presence of a hydrosilylated catalyst of which platinum systemsare represented, with a monomer as represented by formula (1) beingobtained. At this time, a chlorosilane compound can be used instead ofthe compound represented by formula (15). When a chlorosilane compoundis used, the monomer represented by formula (1) can be obtained bycondensing the chlorosilane addition product that is obtained with analkoxysilane compound or a chlorosilane compound in the presence ofwater.

Further, the following method can be presented as an example of thesynthesis of monomers represented by formula (2). First, a compoundrepresented by formula (16):

-   -   wherein, in formula (16), R is H or a methyl group and m′ is an        integer or 2 to 10,        is reacted with a compound represented by the aforementioned        formula (12), in the presence of a base such as potassium        hydroxide or sodium hydride, and a compound represented by        formula (17) is obtained:

-   -   wherein, in formula (17), R is H or a methyl group, m′ is an        integer of 2 to 10, and n is an integer of 2 to 10.        Next, the compound represented by formula (17) is reacted with a        suitable compound having carbon-carbon unsaturated bonds, by        which means a compound represented by formula (18) is obtained.

The suitable compound having carbon-carbon unsaturated bonds differsdepending on the type of X. For example, when X is a group representedby formula (4), it is the corresponding epoxy compound, when X aregroups represented by formula (5), formula (8) and formula (9), it isthe corresponding halide and when X are groups represented by formula(6) and formula (7), it is the corresponding isocyanate compound. Next,the compound represented by formula (18) is reacted with the compoundrepresented by the aforementioned formula (15) in the presence of ahydrosilylated catalyst of which platinum systems are representatives,and a monomer as represented by formula (2) is obtained. At this time, achlorosilane compound can be used instead of the compound represented byformula (15). When a chlorosilane compound is used, the monomerrepresented by formula (2) can be obtained by condensing thechlorosilane addition product that is obtained with an alkoxysilanecompound or a chlorosilane compound in the presence of water.

The polymers of this invention can be obtained by polymerizing themonomers represented by formulas (1) or (2) individually or they can beobtained by copolymerization with other monomers. In the case ofcopolymerization with other monomers, there are no particularlimitations on the copolymerization monomers as long as they can becopolymerized, and monomers having (meth)acryloyl groups, styryl groups,allyl groups, vinyl groups and other copolymerizable carbon-carbonunsaturated bonds can be used.

We shall now present several examples of suitable other monomers.However, they are not limited to these examples. They can include(meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, vinylbenzoic acid; alkyl(meth)acrylates such as methyl (meth)acrylate andethyl(meth)acrylate; polyfunctional (meth)acrylates such as polyalkyleneglycol mono(meth)acrylate, polyalkylene glycolmonoalkylether(meth)acrylate, polyalkylene glycol bis(meth)acrylate,trimethylolpropanetris(meth)acrylate,pentaerythritoltetrakis(meth)acrylate and siloxane macromers havingcarbon-carbon unsaturated bonds in both terminals; halogenatedalkyl(meth)acrylates such as trifluoroethyl(meth)acrylate andhexafluoroisopropyl(meth)acrylate; hydroxyalkyl(meth)acrylates havinghydroxy groups such as 2-hydroxyethyl(meth)acrylate and2,3-dihydroxypropyl(meth)acrylate; (meth)acrylamides such asN,N-dimethyl acrylamide, N,N-diethyl acrylamide, N,N-di-n-propylacrylamide, N,N-diisopropyl acrylamide, N,N-di-n-butyl acrylamide,N-acryloyl morpholine, N-acryloyl piperidine, N-acryloyl pyrrolidine andN-methyl(meth)acrylamide; aromatic vinyl monomers such as styrene,α-methylstyrene and vinyl pyridine; maleimides; heterocyclic vinylmonomers such as N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyloxasolidone, 1-vinyl imidazole, N-vinyl carbazole, vinyl pyridine andvinyl pyrazine; N-vinyl carboxamides such as N-vinyl formamide, N-vinylacetamide and N-methyl-N-vinyl acetamide; vinyl esters such as vinylacetate; 3-[tris(trimethylsiloxy)silyl]propyl(meth)acrylate,3-[bis(trimethylsiloxy)methylsilyl]propyl(meth)acrylate,3-[(trimethylsiloxy)dimethylsilyl]propyl(meth)acrylate,3-[tris(trimethylsiloxy)silyl]propyl(meth)acrylamide,3-[bis(trimethylsiloxy)methylsilyl]propyl(meth)acrylamide,3-[(trimethylsiloxy)dimethylsilyl]propyl(meth)acrylamide,[tris(trimethylsiloxy)silyl]methyl(meth)acrylate,[bis(trimethylsiloxy)methylsilyl]methyl(meth)acrylate,[(trimethylsiloxy)dimethylsilyl]methyl(meth)acrylate,[tris(trimethylsiloxy)silyl]methyl(meth)acrylamide,[bis(trimethylsiloxy)methylsilyl]methyl(meth)acrylamide,[(trimethylsiloxy)dimethylsilyl]methyl(meth)acrylamide,[tris(trimethylsiloxy)silyl]styrene,[bis(trimethylsiloxy)methylsilyl]styrene,[(trimethylsiloxy)dimethylsilyl]styrene,N-[3-[tris(trimethylsiloxy)silyl]propyl]vinyl carbamide,N-[3-[bis(trimethylsiloxy)methylsilyl]propyl]vinyl carbamide,N-[3-[(trimethylsiloxy)dimethylsilyl]propyl]vinyl carbamide andcompounds of formulas (19) to (21) indicated below:

-   -   wherein, in formulas (19) to (21), R¹¹ is H or a methyl group        and s is an integer of 1 to 3.

For the purpose of obtaining good mechanical properties and of obtaininggood resistance to disinfecting solutions and washing solutions, in thepolymer of this invention, it is desirable to use monomers having two ormore copolymerizable carbon-carbon unsaturated bonds in one molecule ascopolymerization components. The copolymerization ratio of monomershaving two or more copolymerizable carbon-carbon unsaturated bonds inone molecule should be 0.1 weight % to 70 weight %, and, preferably, 0.2weight % to 40 weight %.

From the standpoint of achieving both high oxygen permeability and highwater content, it is desirable to copolymerize and use monomersrepresented by formula (1) or (2) for the polymers of this invention. Inthis case, the copolymerization ratio of monomers represented by formula(1) or (2) should be 30 weight % to 97 weight %, preferably, 50 weight %to 95 weight %, and, more preferably, 60 weight % to 90 weight %. Whenthe copolymerization ratio of the monomers represented by formula (1) or(2) is too low, oxygen permeability of the polymer is decreased. When itis too high, there is a tendency for water content to decrease.

The polymers of this invention may also contain ultraviolet absorbents,pigments and colorants. Ultraviolet absorbents, pigments and colorantshaving polymerizable groups may also be present in copolymerized form.

When the polymers of this invention are obtained by (co)polymerization,thermal polymerization initiators and photopolymerization initiators, ofwhich peroxides and azo compounds are representative, may be added tofacilitate polymerization. When thermal polymerization is performed,substances having optimum dissolution properties at the desired reactiontemperature are selected and used. In general, azo initiators andperoxide initiators having 10 hours half-life temperatures of 40 to 120°C. are desirable. Carbonyl compounds, peroxides, azo compounds, sulfurcompounds, halides and metal salts can be cited as photopolymerizationinitiators. These polymerization initiators can be used individually orin mixtures and are used in quantities up to about 1 weight %.

Polymerization solvents can be used when the polymers of this inventionare obtained by (co)polymerization. Various organic and inorganicsolvents can be used as solvents and there are no particular limitationson them. Examples that can be cited include water, alcohol solvents suchas methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropylalcohol, normal butyl alcohol, isobutyl alcohol and tert-butyl alcohol;glycol ether solvents such as methyl cellosolve, ethyl cellosolve,isopropyl cellosolve, butyl cellosolve, propylene glycol monomethylether, ethylene glycol dimethyl ether, diethylene glycol dimethyl etherand triethylene glycol dimethyl ether; ester solvents such as ethylacetate, butyl acetate, amyl acetate, ethyl lactate and methyl benzoate;aliphatic hydrocarbon solvents such as normal hexane, normal heptane andnormal octane; alicyclic hydrocarbon solvents such as cyclohexane andethyl cyclohexane; ketone solvents such as acetone, methyl ethyl ketoneand methyl isobutyl ketone; aromatic hydrocarbon solvents such asbenzene, toluene and xylene; and petroleum solvents. They can be usedindividually or in mixtures.

Known polymerization methods and molding methods can be used for thepolymers of this invention. For example, there is a method in which theyare polymerized and molded into rods or plates and are processed to thedesired shapes by cutting and processing, a mold polymerization methodand a spin cast polymerization method.

As an example, we shall now describe the case in which the polymers ofthis invention are obtained by the mold polymerization method.

A monomer composition is filled into the space of two molds having afixed shape. Photopolymerization or thermal polymerization is performedand it is formed to the shape of the mold. The mold can be made ofresin, glass, ceramics or metal. In the case of photopolymerization, amaterial that is optically transparent is used, and, ordinarily, resinor glass is used. In many cases, when the polymer is manufactured, aspace is formed by the two opposing molds and the space is filled withthe monomer composition. Depending on the shape of the mold and theproperties of the monomer, a gasket may be used for the purpose ofconferring a fixed thickness on the polymer and of preventing leakage ofthe filled monomer composition. The mold into the space of which themonomer composition is filled, is then irradiated with active light rayssuch as ultraviolet rays or is introduced into an oven or water bath oroil bath to heat and polymerize. The two methods can also be used incombination, with thermal polymerization being performed afterphotopolymerization, or, conversely, photopolymerization can beperformed after thermal polymerization. In the case ofphotopolymerization, for example, light containing a large portion ofultraviolet rays is usually irradiated for a short time (ordinarily 1hour or less) using a mercury lamp or an insect attraction lamp as thelight source. When thermal polymerization is performed, the temperatureis gradually raised from close to room temperature, being increased to atemperature of 60° C. to 200° C. over a period of several hours toseveral tens of hours. These conditions are desirable for the purpose ofmaintaining the optical homogeneity and quality of the polymer and ofincreasing reproducibility.

The polymers of this invention can be subjected to modificationtreatments by various methods. It is desirable to perform saidmodification treatments for the purpose of increasing surfacewettability.

Specific modification methods of polymers can include electromagneticwaves (including light) irradiation, plasma irradiation, chemical vapordeposition treatments such as vaporization and sputtering, heating,treatment with bases, treatment with acids and the use of other suitablesurface treatment agents, and combinations of these treatments. Of thesemodification procedures, treatment with bases and treatment with acidsare desirable because they are simple.

Examples of treatments with bases or treatments with acids that can becited include a method in which the polymer is brought into contact witha basic or acidic solution and a method in which the polymer is broughtinto contact with a basic or acidic gas. More specific examples of thesemethods include, for example, methods in which the polymer is immersedin a basic or acidic solution, methods in which a basic or acidicsolution or basic or acidic gas is sprayed at the polymer, methods inwhich the basic or acidic solution is applied to the polymer with aspatula or brush and methods in which the basic or acidic solution isapplied to the polymer by a spin coating method or a dip coating method.The method whereby great modifying effects can be obtained most simplyis the method in which the polymer is immersed in the basic or acidicsolution.

There are no particular limitations on temperature when the polymer isimmersed in the basic or acidic solution. However, the procedure isusually performed in a temperature range of approximately −50° C. to300° C. When workability is considered, a temperature range of −10° C.to 150° C. is preferable and −5° C. to 60° C. is more preferable.

The optimum period for immersion of the polymer in the basic or acidicsolution varies depending on the temperature. In general, a period of upto 100 hours is desirable, a period of up to 24 hours is more preferableand a period of up to 12 hours is most preferable. When contact time istoo long, workability and productivity deteriorate and there areinstances in which there are such deleterious effects as decrease ofoxygen permeability and decrease of mechanical properties.

The bases that can be used include alkali metal hydroxides, alkalineearth metal hydroxides, various carbonates, various borates, variousphosphates, ammonia, various ammonium salts, various amines and highmolecular weight bases such as polyethylene imines and polyvinyl amines.Of these, alkali metal hydroxides are the most desirable because theyare inexpensive and very effective.

The acids that can be used include various inorganic acids such assulfuric acid, phosphoric acid, hydrochloric acid and nitric acid,various organic acids such as acetic acid, formic acid, benzoic acid andphenol and high molecular weight acids such as polyacrylic acids,polymethacrylic acids, polystyrene sulfonic acids and polysulfomethylstyrene. Of these, high molecular weight acids are the most desirablebecause of their great treatment effectiveness and little deleteriouseffect on other physical properties.

Various inorganic and organic solvents can be used as solvents of thebasic or acidic solution. For example, they can include water; variousalcohols such as methanol, ethanol, propanol, 2-propanol, butanol,ethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, polyethylene glycol and glycerol; various aromatic hydrocarbonssuch as benzene, toluene and xylene; various aliphatic hydrocarbons suchas hexane, heptane, octane, decane, petroleum ether, kerosene, ligroinand paraffin; various ketones such as acetone, methyl ethyl ketone andmethyl isobutyl ketone; various esters such as ethyl acetate, butylacetate, methyl benzoate and dioctyl phthalate; various ethers such asdiethyl ether, tetrahydrofuran, dioxane, ethylene glycol dialkyl ether,diethylene glycol dialkyl ether, triethylene glycol dialkyl ether,tetraethylene glycol dialkyl ether and polyethylene glycol dialkylether; various nonprotonic polar solvents such as dimethylformamide,dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone,hexamethyl phosphoric triamide and dimethyl sulfoxide; halogen solventssuch as methylene chloride, chloroform, dichloroethane trichloroethaneand trichloroethylene; and freon solvents. Of these, water is the mostdesirable from the standpoints of economic factors, convenience ofhandling and chemical stability. These solvents can also be used inmixtures of two or more.

The basic or acidic solutions that are used in this invention may alsocontain components other than the basic substances or acidic substancesand the solvents.

In this invention, after the polymer has been subjected to treatmentwith a base or an acid, the basic or acidic substance can be removed bywashing.

Various inorganic and organic solvents can be used as washing solvents.For example, they can include water; various alcohols such as methanol,ethanol, propanol, 2-propanol, butanol, ethylene glycol, diethyleneglycol, triethylene glycol, tetraethylene glycol, polyethylene glycoland glycerol; various aromatic hydrocarbons such as benzene, toluene andxylene; various aliphatic hydrocarbons such as hexane, heptane, octane,decane, petroleum ether, kerosene, ligroin and paraffin; various ketonessuch as acetone, methyl ethyl ketone and methyl isobutyl ketone; variousesters such as ethyl acetate, butyl acetate, methyl benzoate and dioctylphthalate; various ethers such as diethyl ether, tetrahydrofuran,dioxane, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether,triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether andpolyethylene glycol dialkyl ether; various nonprotonic polar solventssuch as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone,dimethylimidazolidinone, hexamethyl phosphoric triamide and dimethylsulfoxide; halogen solvents such as methylene chloride, chloroform,dichloroethane trichloroethane and trichloroethylene; and freonsolvents. Generally, water is the most desirable.

Mixtures of two or more of these solvents can be used as the washingsolvent. The washing solvent may also contain components other than thesolvents, for example, inorganic salts, surfactants and detergents.

The entire polymer may be subjected to said modification treatment or itmay be performed on only a portion of the polymer, for example, thesurface. When only the surface is subjected to modification treatment,wettability of the surface can be improved without making great changesin the polymer as a whole.

The oxygen permeability coefficient of the polymer of this inventionshould be greater than 50×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)], preferably,greater than 55×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)], and, most preferably,greater than 60×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)] in terms of the oxygenpermeability. By setting the oxygen permeability coefficient in thisrange, the burden on the eyes can be decreased and continuous wearing isfacilitated when used as contact lenses.

The water content should be 15 weight % to 60 weight %, preferably, 20weight % to 55 weight %, and, more preferably, 25 weight % to 50 weight%. When the water content is greater than 15 weight %, its action in theeyes is improved when used as a contact lens and continuous wearing isfacilitated. When the water content is excessively high, the oxygenpermeability coefficient is decreased, for which reason this is notdesirable.

The modulus of elasticity should be 65 kPa to 2000 kPa, preferably, 100kPa to 1400 kPa, and, most preferably, 150 kPa to 850 kPa. When themodulus of elasticity is excessively low, the polymer is too soft, sothat its shape-maintaining capacity deteriorates and it is difficult tohandle, for which reason this is not desirable. When the modulus ofelasticity is excessively high, the polymer is excessively hard and,when it is used as a contact lens, comfort on wearing deteriorates, forwhich reason this is not desirable.

The monomers and polymers of this invention are particularly suited forophthalmic lenses such as contact lenses, intraocular lenses andartificial corneas.

We shall now describe this invention in specific terms by means ofexamples. However, this invention is not limited by them.

Determination Methods

The various determinations in these examples were performed by themethods described below.

(1) Proton Nuclear Magnetic Resonance Spectrum

Determinations were performed using Model EX270 manufactured by JEOLLtd. Chloroform-d was used as the solvent. The chloroform peak was takenas the internal standard (7.26 ppm).

(2) Oxygen Permeability Coefficient

The oxygen permeability coefficient of a sample in the shape of acontact lens was determined in water of 35° C. using a Seikaken-shikifilm oxygen permeability meter manufactured by RIKA SEIKI KOGYO Co.,Ltd. The film thickness of the sample was controlled according tonecessity by overlapping plurality of films.

(3) Water Content

A sample in the form of a contact lens was used. The sample was driedfor 16 hours at 40° C. in a vacuum dryer and the weight (Wd) of thesample was determined. Following that, it was immersed in pure water andwas impregnated with water overnight in a constant temperature tank at40° C., after which the water on the surface was wiped off with Kimwipeand its weight (Ww) was measured. The water content was found by thefollowing formula.Water content(%)=100×(Ww−Wd)/Ww(4) Modulus of Elasticity

A sample [width (smallest part), 5 mm; length, 14 mm; thickness, about0.2 mm] cut from a substance in the contact lens shape using astipulated punch mold was used, and determinations were made using ModelRTM-100 TENSILON manufactured by Orientec Corporation. The drawing ratewas set to 100 mm/min and the distance between grips was set to 5 mm.

EXAMPLE 1

Synthesis of the Compound Represented by Formula (22)

(1) 1,3-propanediol (100 g) and potassium hydroxide (86.7 g) wereintroduced into a 500 mL three-neck distillation flask equipped with adropping funnel, a reflux condenser and a stirring blade, and themixture was stirred for about 1 hour at room temperature. Allyl bromide(159 g) was introduced through the dropping funnel and was addeddropwise while the mixture was being stirred. After the dropwiseaddition had been completed, a reaction was carried out for 3 hours at60° C. as the mixture was being stirred. Diethyl ether (250 mL) wasadded, after which the salt was removed by filtration and the solventcomponent was removed with a rotary vacuum evaporator. Because the saltagain precipitated, it was removed by filtration. Purification wasperformed by distillation under reduced pressure and 3-allyloxypropanolwas obtained as a colorless, transparent liquid.

(2) The 3-allyloxypropanol (15 g) that was synthesized in (1),triethylamine (19.6 g) and tetrahydrofuran (30 mL) were introduced intoa 300 mL three-neck distillation flask equipped with a dropping funneland a stirring blade. The three neck distillation flask was immersed inan ice bath and methacrylic acid chloride (20.2 g) was added dropwiseover a period of approximately 30 minutes as the mixture was beingstirred. After the dropwise addition was completed, stirring wascontinued for 2 hours at room temperature. The salt that precipitatedwas removed by suction and filtration. Ethyl acetate (100 mL) was addedto the filtrate which was then introduced into a separatory funnel andwashed using a saline solution, saturated aqueous solution of sodiumhydrogen carbonate and saline solution in that order. Dehydrationtreatment was performed with anhydrous magnesium sulfate, after whichthe solvent was removed with a rotary vacuum evaporator. Purificationwas performed by distillation under reduced pressure and3-allyloxypropyl methacrylate was obtained as a colorless, transparentliquid.

(3) Chloroplatinic acid 6-hydrate was dissolved in an equal volume of2-propanol and was diluted to 1.93×10⁻⁵ mol/g with tetrahydrofuran.Hereafter, this solution is called the “catalyst solution.”

The 3-allyloxypropyl methacrylate (6.94 g) that was synthesized in (2),toluene (12 g) and the catalyst solution (3.9 g) were introduced into a100 mL eggplant type flask equipped with a magnetic rotor. The flask wasimmersed in a water bath and was cooled, and trichlorosilane (10.21 g)was added in small amounts at a time as the mixture was being stirred.After it was confirmed that generation of heat stopped, the flask washermetically sealed with a septum and was allowed to stand overnight atroom temperature. The low boiling point components were removed by meansof a rotary vacuum evaporator, after which purification was performed bydistillation under reduced pressure and 3-(3-methacryloxypropoxy) propyltrichlorosilane was obtained as a colorless, transparent liquid.

(4) Hexane (2.4 g), methanol (2.4 g), and water (4.8 g) were introducedinto a 200 mL eggplant type flask equipped with a magnetic rotor, theflask was immersed in an ice bath and the contents of the flask werestirred vigorously. A mixture consisting of the3-(3-methacryloxypropoxy)propyl trichlorosilane (4.58 g) synthesized in(3) and methoxytrimethyl silane (8.94 g) was added dropwise over aperiod of approximately 10 minutes. After the dropwise addition wascompleted, stirring was continued for 4 hours at room temperature. Thereaction solution was separated into two layers and the top layer wascollected with a separatory funnel. It was washed using a saturatedaqueous solution of sodium hydrogen carbonate (3 times) and water (2times) in that order. Dehydration was performed with anhydrous sodiumsulfate, after which the solvent was removed with a rotary vacuumevaporator. Purification was performed by distillation under reducedpressure and a pale yellow transparent liquid was obtained. The protonnuclear magnetic resonance spectrum of this liquid was determined andanalyzed. As a result, peaks were detected in the vicinity of 0.1 ppm(27H), in the vicinity of 0.4 ppm (2H), in the vicinity of 1.6 ppm (2H),in the vicinity of 1.9 ppm (5H), in the vicinity of 3.3 ppm (2H), in thevicinity of 3.5 ppm (2H), in the vicinity of 4.2 ppm (2H), in thevicinity of 5.5 ppm (1H) and in the vicinity of 6.1 ppm (1H). From thesefindings, it was confirmed that this was the compound represented byformula (22).

EXAMPLE 2

Synthesis of the Compound Represented by Formula (23)

A pale yellow transparent liquid was obtained in the same way as inExample 1 except that acrylic acid chloride was used instead ofmethacrylic acid chloride. The proton nuclear magnetic resonancespectrum of this liquid was determined and analyzed. As a result, peakswere detected in the vicinity of 0.1 ppm (27H), in the vicinity of 0.4ppm (2H), in the vicinity of 1.6 ppm (2H), in the vicinity of 1.9 ppm(2H), in the vicinity of 3.3 ppm (2H). in the vicinity of 3.5 ppm (2H),in the vicinity of 4.2 ppm (2H), in the vicinity of 5.8 ppm (1H), in thevicinity of 6.2 ppm (1H) and in the vicinity of 6.4 ppm (1H). From thesefindings, it was confirmed that this was the compound represented byformula (23).

EXAMPLE 3

The compound of formula (22) (65 parts by weight) obtained in Example 1,N,N-dimethyl acrylamide (35 parts by weight), triethylene glycoldimethacrylate (1 part by weight), Darocure 1173 (manufactured by CIBASpecialty Chemicals Inc., 0.5 part by weight) and diethylene glycoldimethyl ether (10 parts by weight) were mixed and stirred. Ahomogeneous, transparent monomer mixture was obtained, and this monomermixture was deaerated in an argon atmosphere. It was poured into acontact lens mold made of transparent resin (poly 4-methylpentene-1) ina glove box in a nitrogen atmosphere, polymerization was performed byirradiation (1 mW/cm², 10 minutes) using an insect attraction lamp, anda contact lens-shaped sample was obtained. It was immersed for 16 hoursat 60° C. in a large excess volume of isopropyl alcohol, after which itwas immersed for 24 hours in a large excess volume of pure water.Following that, it was immersed and stored in clear, pure water. Thesample that was obtained was transparent and was not turbid. The oxygenpermeability coefficient of this sample was 70×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)], its water content was 30% and its modulus of elasticitywas 380 kPa. Thus, it had high oxygen permeability, high water contentand a low modulus of elasticity.

EXAMPLE 4

A contact lens-shaped sample was obtained in the same way as in Example3 except that the compound of formula (23) (35 parts by weight) obtainedin Example 2 and 3-methacryloxypropyltris(trimethylsiloxy)silane (30parts by weight) were used instead of the compound of formula (22) (65parts by weight). The sample that was obtained was transparent and wasnot turbid. The oxygen permeability coefficient of this sample was75×10⁻¹¹ (cm²/sec) [mLO₂/(mL·hPa)], its water content was 26% and itsmodulus of elasticity was 280 kPa. Thus, it had high oxygenpermeability, high water content and a low modulus of elasticity.

EXAMPLE 5

Synthesis of the Compound Represented by Formula (24)

(1) Diethylene glycol (100 g) and potassium hydroxide (62.2 g) wereintroduced into a 500 mL three-neck distillation flask equipped with adropping funnel, a reflux condenser and a stirring blade, and themixture was stirred for about 1 hour at room temperature. Allyl bromide(114 g) was introduced through the dropping funnel and was addeddropwise while the mixture was being stirred. After the dropwiseaddition had been completed, a reaction was carried out for 3 hours at60° C. as the mixture was being stirred. Diethyl ether (250 mL) wasadded, after which the salt was removed by filtration and the solventcomponent was removed with a rotary vacuum evaporator. Because the saltagain precipitated, it was removed by filtration. Purification wasperformed by distillation under reduced pressure, and diethylene glycolmonoallyl ether was obtained as a colorless, transparent liquid.

(2) The diethylene glycol monoallyl ether (20 g) that was synthesized in(1), triethylamine (20.7 g) and tetrahydrofuran (30 mL) were introducedinto a 300 mL three-neck distillation flask equipped with a droppingfunnel and a stirring blade. The three-neck distillation flask wasimmersed in an ice bath and methacrylic acid chloride (21.4 g) was addeddropwise over a period of approximately 5 minutes as the mixture wasbeing stirred. After the dropwise addition was completed, stirring wascontinued for 3 hours at room temperature. The salt that precipitatedwas removed by suction and filtration. Ethyl acetate (100 mL) was addedto the filtrate which was then introduced into a separatory funnel andwas washed using a saline solution, saturated aqueous solution of sodiumhydrogen carbonate and saline solution in that order. Dehydrationtreatment was performed with anhydrous magnesium sulfate, after whichthe solvent was removed with a rotary vacuum evaporator. Purificationwas performed by distillation under reduced pressure and2-(2-allyloxyethoxy)ethyl methacrylate was obtained as a colorless,transparent liquid.

(3) The 2-(2-allyloxyethoxy)ethyl methacrylate (13.63 g) that wassynthesized in (2), toluene (13 g) and the catalyst solution (6.6 g)were introduced into a 100 mL eggplant type flask equipped with amagnetic rotor. The flask was immersed in a water bath and was cooled,and trichlorosilane (17.22 g) was added in small amounts at a time asthe mixture was being stirred. After it was confirmed that generation ofheat stopped, the flask was hermetically sealed with a septum and wasallowed to stand overnight at room temperature. The low boiling pointcomponents were removed by means of a rotary vacuum evaporator, afterwhich purification was performed by distillation under reduced pressureand 3-[2-(2-methacryloxyethoxy)ethoxy] propyl trichlorosilane wasobtained as a colorless, transparent liquid.

(4) Hexane (6.0 g), methanol (6.0 g) and water (12.0 g) were introducedinto a 200 mL eggplant type flask equipped with a magnetic rotor, theflask was immersed in an ice bath and the contents of the flask werestirred vigorously. A mixture consisting of3-[2-(2-methacryloxyethoxy)ethoxy]propyl trichlorosilane (12.5 g) andmethoxytrimethyl silane (22.3 g) was added dropwise over a period ofapproximately 10 minutes. After the dropwise addition was completed,stirring was continued for 3.5 hours at room temperature. The reactionsolution was separated into two layers and the top layer was collectedwith a separatory funnel. It was washed using a saturated aqueoussolution of sodium hydrogen carbonate (3 times) and water (2 times) inthat order. Dehydration was performed with anhydrous sodium sulfate,after which the solvent was removed with a rotary vacuum evaporator.Purification was performed by distillation under reduced pressure and apale yellow transparent liquid was obtained. The proton nuclear magneticresonance spectrum of this liquid was determined and analyzed. As aresult, peaks were detected in the vicinity of 0.1 ppm (27H), in thevicinity of 0.4 ppm (2H), in the vicinity of 1.6 ppm (2H), in thevicinity of 1.9 ppm (3H), in the vicinity of 3.4 ppm (2H), in thevicinity of 3.5 to 3.8 ppm (6H), in the vicinity of 4.3 ppm (2H), in thevicinity of 5.5 ppm (1H) and in the vicinity of 6.1 ppm (1H). From thesefindings, it was confirmed that this was the compound represented byformula (24).

EXAMPLE 6

Synthesis of the Compound Represented by Formula (25)

A pale yellow transparent liquid was obtained in the same way as inExample 1 except that acrylic acid chloride was used instead ofmethacrylic acid chloride. The proton nuclear magnetic resonancespectrum of this liquid was determined and analyzed. As a result, peakswere detected in the vicinity of 0.1 ppm (27H), in the vicinity of 0.4ppm (2H), in the vicinity of 1.6 ppm (2H), in the vicinity of 3.4 ppm(2H), in the vicinity of 3.5 to 3.8 ppm (6H), in the vicinity of 4.3 ppm(2H), in the vicinity of 5.8 ppm (1H), in the vicinity of 6.2 ppm (1H)and in the vicinity of 6.4 ppm (1H). From these findings, it wasconfirmed that this was the compound represented by formula (25).

EXAMPLE 7

The compound of formula (24) (65 parts by weight) obtained in Example 1,N,N-dimethyl acrylamide (35 parts by weight), triethylene glycoldimethacrylate (1 part by weight), Darocure 1173 (manufactured by CIBASpecialty Chemicals Inc., 0.5 part by weight) and diethylene glycoldimethyl ether (10 parts by weight) were mixed and stirred. Ahomogeneous, transparent monomer mixture was obtained. This monomermixture was deaerated in an argon atmosphere. It was then poured into acontact lens mold made of transparent resin (poly 4-methylpentene-1) ina glove box in a nitrogen atmosphere, polymerization was performed byirradiation (1 mW/cm², 10 minutes) using an insect attraction lamp, anda contact lens-shaped sample was obtained. It was immersed for 16 hoursat 60° C. in a large excess volume of isopropyl alcohol, after which itwas immersed for 24 hours in a large excess volume of pure water.Following that, it was immersed and stored in clear, pure water. Thesample that was obtained was transparent and was not turbid. The oxygenpermeability coefficient of this sample was 69×10⁻¹¹ (cm²/sec)[mLO₂/(mL·hPa)], its water content was 39% and its modulus of elasticitywas 180 kPa. Thus, it had high oxygen permeability, high water contentand a low modulus of elasticity.

EXAMPLE 8

A contact lens-shaped sample was obtained in the same way as in Example7 except that the compound of formula (25) (35 parts by weight) obtainedin Example 2 and 3-methacryloxypropyltris(trimethylsiloxy)silane (30parts by weight) were used instead of the compound of formula (24) (65parts by weight). The sample that was obtained was transparent and wasnot turbid. The oxygen permeability coefficient of this sample was74×10⁻¹¹ (cm²/sec) [mLO₂/(mL·hPa)], its water content was 38% and itsmodulus of elasticity was 280 kPa. Thus, it had high oxygenpermeability, high water content and a low modulus of elasticity.

COMPARATIVE EXAMPLE 1

A contact lens-shaped sample was obtained in the same way as in Example3 except that 3-methacryloxypropyltris(trimethylsiloxy)silane (65 partsby weight) was used instead of the compound of formula (22) (65 parts byweight). The sample that was obtained was transparent and was notturbid. The oxygen permeability coefficient of this sample was 83×10⁻¹¹(cm²/sec) [mLO₂/(mL·hPa)], its water content was 22% and its modulus ofelasticity was 2050 kPa. Although it had high oxygen permeability, itswater content was lower and its modulus of elasticity was higher than inExample 3, Example 4, Example 7 and Example 8.

COMPARATIVE EXAMPLE 2

A contact lens-shaped sample was obtained in the same way as in Example3 except that the compound represented by formula (10) (65 parts byweight) was used instead of the compound of formula (22) (65 parts byweight). The sample that was obtained was transparent and was notturbid. The oxygen permeability coefficient of this sample was 71×10⁻¹¹(cm²/sec) [mLO₂/(mL·hPa)], its water content was 25% and its modulus ofelasticity was 830 kPa. Although it had high oxygen permeability and ahigh water content, its modulus of elasticity was higher than in Example3, Example 4, Example 7 and Example 8.

INDUSTRIAL APPLICABILITY

By means of monomers of this invention, polymers and ophthalmic lenseshaving high oxygen permeability, high water content and a low modulus ofelasticity are obtained.

1. A monomer that is represented by formula (1) or (2) below:X—O—(CH₂CH₂CH₂O)_(m)—(CH₂)_(n)—A  (1)

wherein, A is a siloxanyl group; R is H or a methyl group; m is aninteger of 1 to 10; m′ is an integer of 2 to 10; and n is an integer of2 to 10 and X is one substituent selected from substituents asrepresented by formulas (4) to (9) below:

wherein, in formulas (4) to (9), R¹ is H or a methyl group.
 2. Themonomer of claim 1 wherein the aforementioned siloxanyl group is asubstituent as represented by formula (3) below:

wherein, in formula (3), A¹ to A¹¹, respectively and independently, areH, alkyl groups of 1 to 20 carbon atoms that may be substituted or arylgroups of 6 to 20 carbon atoms that may be substituted; k is an integerof 0 to 200; and a, b and c, respectively and independently, areintegers of 0 to 20, excepting the case k=a=b=c=0.
 3. A monomer that isrepresented by formula (1) or (2) below:X—O—(CH₂CH₂CH₂O)_(m)—(CH₂)_(n)—A  (1)

wherein, X is a polymerizable group having carbon-carbon unsaturatedbonds; A is a siloxanyl group; R is a methyl group; m is an integer of 1to 10; m′ is an integer of 2 to 10; and n is an integer of 2 to
 10. 4.The monomer of claim 3 wherein the aforementioned siloxanyl group is asubstituent as represented by formula (3) below:

wherein, in formula (3), A¹ to A¹¹, respectively and independently, areH, alkyl groups of 1 to 20 carbon atoms that may be substituted or arylgroups of 6 to 20 carbon atoms that may be substituted; k is an integerof 0 to 200; and a, b and c, respectively and independently, areintegers of 0 to 20, excepting the case k=a=b=c=0.
 5. The monomer ofclaim 3 wherein X in formula (1) or (2) is one substituent selected fromsubstituents as represented by formulas (4) to (9) below:

wherein, in formulas (4) to (9), R¹ is H or a methyl group.
 6. Themonomer of claim 3 wherein, said monomer is represented by formula (1),and X is a methacryloyl group or an acryloyl group, A is one substituentselected from tris(trimethylsiloxy)silyl groups,methylbis(trimethylsiloxy)silyl groups anddimethyl(trimethylsiloxy)silyl groups, m is an integer of 1 or 2 and nis an integer of
 3. 7. A monomer represented by formula (2),X—O—(CH₂—CHR—O)_(m′)—(CH_(n))_(n)—A  (2) wherein X is a methacryloylgroup or an acryloyl group, R is H, A is one substituent selected fromtris(trimethylsiloxy)silyl groups, methylbis(trimethylsiloxy)silylgroups and dimethyl(trimethylsiloxy)silyl groups, m′ is an integer of 2or 3 and n is an integer of 3.